University of Groningen

Reactive extraction of lactic acid using alamine 336 in MIBK

Wasewar, Kailas L.; Heesink, A. Bert M.; Versteeg, Geert F.; Pangarkar, Vishwas G.

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Journal of Biotechnology

DOI:
10.1016/S0168-1656(02)00057-3

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Wasewar, K. L., Heesink, A. B. M., Versteeg, G. F., & Pangarkar, V. G. (2002). Reactive extraction of lactic
acid using alamine 336 in MIBK: equilibria and kinetics. Journal of Biotechnology, 97(1), 59-68.
https://doi.org/10.1016/S0168-1656(02)00057-3

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 Journal of Biotechnology 97 (2002) 59 – 68
www.elsevier.com/locate/jbiotec

Reactive extraction of lactic acid using alamine 336 in

MIBK: equilibria and kinetics
Kailas L. Wasewar a, A. Bert M. Heesink b, Geert F. Versteeg b,
Vishwas G. Pangarkar a,*
a
Mumbai Uni6ersity Institute of Chemical Technology, Matunga, Mumbai 400 019, India
b
Department of Chemical Engineering, Uni6ersity of Twente, 7500 AE Enschede, Netherlands
Received 16 October 2001; received in revised form 7 March 2002; accepted 15 March 2002

Abstract

Lactic acid is an important commercial product and extracting it out of aqueous solution is a growing requirement
in fermentation based industries and recovery from waste streams. The design of an amine extraction process requires
(i) equilibrium and (ii) kinetic data for the acid–amine (solvent) system used. Equilibria for lactic acid extraction by
alamine 336 in methyl-iso-butyl-ketone (MIBK) as a diluent have been determined. The extent to which the organic
phase (amine +MIBK) may be loaded with lactic acid is expressed as a loading ratio, z= [HL]o/[B]i,o. Calculations
based on the stoichiometry of the reactive extraction and the equilibria involved indicated that more lactic acid is
transferred to the organic phase than would be expected from the (1:1) stoichiometry of the reaction. The extraction
equilibrium was interpreted as a result of consecutive formation of two acid– amine species with stoichiometries of 1:1
and 2:1. Equilibrium complexation constant for (1:1) and (2:1) has been estimated. Kinetics of extraction of lactic acid
by alamine 336 in MIBK has also been determined. In a first study of its kind, the theory of extraction accompanied
by a chemical reaction has been used to obtain the kinetics of extraction of lactic acid by alamine 336 in MIBK. The
reaction between lactic acid and alamine 336 in MIBK in a stirred cell falls in Regime 3, extraction accompanied by
a fast chemical reaction occurring in the diffusion film. The reaction has been found to be zero order in alamine 336
and first order in lactic acid with a rate constant of 1.38 s − 1. These data will be useful in the design of extraction
processes. © 2002 Elsevier Science B.V. All rights reserved.

Keywords: Lactic acid; Reactive extraction; Alamine 336; MIBK; Equilibria; Kinetics

1. Introduction tic acid is an important chemical, which can be

Lactic acid is a commodity chemical utilized in
the food, chemical and pharmaceutical fields. Lac-
* Corresponding author. Tel.: +91-22-414-5616; fax: + 91-
22-414-5614.
E-mail address: vgp@udct.ernet.in (V.G. Pangarkar).
converted to ethanol, propylene glycol, acrylic
polymers and polyesters. In particular an increas-
ingly interesting application is the use of lactic
acid as a monomer for the synthesis of biodegrad-
able homopolymers and copolymers (Buchta,
1983; Datta et al., 1995). Lactic acid is a raw
material for the production of biodegradable

0168-1656/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 8 - 1 6 5 6 ( 0 2 ) 0 0 0 5 7 - 3
60 K.L. Wasewar et al. / Journal of Biotechnology 97 (2002) 59–68
polylactic acid. A growing demand for biodegrad-
able polymers, both substitutes for conventional
plastic materials and new materials of specific uses
such as controlled drug delivery or artificial pros-
theses, draws attention to improved conventional
processes for lactic acid production (Lipinsky and
Sinclair, 1986).
Recovery of lactic acid from aqueous solutions
is a growing requirement in fermentation based
industries and recovery from waste streams. Lac-
tic acid can be produced by the fermentation of
biomass. However the fermentation broth has a
low concentration (B 10%) of lactic acid due to a
product inhibition of the biological process. The
traditional recovery process of lactic acid from
fermentation broth is quite complicated. Isolation
of this acid from dilute wastewater or fermenta-
tion broths is an economic problem since the
vaporization of water consumes much energy and
a direct upgrading of the wastewater by evapora-
tion is inefficient. Lactic acid is non-volatile and
hence distillation is not useful. In conventional
processes, lactic acid has been recovered from the
fermentation broth by precipitation of calcium
lactate with calcium hydroxide. In this recovery
scheme, calcium lactate is precipitated, recovered
by filtration and converted to lactic acid by addi-
tion of sulfuric acid. The dilute lactic acid product
is then sequentially purified using activated car-
bon, evaporation and crystallization. These sepa-
ration and final purification stages account for up
to 50% of the production costs (Chaudhuri and
Pyle, 1992; Eyal and Bressler, 1993). Thus, this
method of recovery is expensive and unfriendly to
the environment as it consumes lime and sulfuric
acid and also produces a large quantity of calcium
sulfate sludge as solid waste (Shreve and Brink,
1977). Allowing accumulation of lactic acid
product in fermentation broth inhibits further
product formation. Reactor productivities are low
and the products are obtained in the dilute form.
The effects of end product inhibition can be re-
duced by in situ removal of lactic acid from
fermentation broth by several methods.
A number of processes for lactic acid recovery
from fermentation broth without precipitation
have been studied and reported in the literature:
solvent extraction (Wardell and King, 1978;
Baniel et al., 1981; Kertes and King, 1986;
Tamada et al., 1990a,b; Yabannavar and Wang,
1991; King, 1992; Tik et al., 2001) membrane
bioreactor (Moueddeb et al., 1996; Jaung and
Huang, 1997; Tong et al., 1998), liquid surfactant
membrane extraction (Baniel, 1982; Sirman et al.,
1991), adsorption (Kaufman et al., 1994), direct
distillation (Cockrem and Johnson, 1991), electro-
dialysis (Hongo et al., 1986; Boyaval et al., 1987;
Lee et al., 1998), chromatographic methods
(Hauer and Marr, 1994), ultrafiltration (Hauer
and Marr, 1994), reverse osmosis (Timmer et al.,
1994), drying (Hauer and Marr, 1994), etc.
Reactive extraction with specified extractant
giving a higher distribution coefficient has been
proposed as a promising technique for the recov-
ery of carboxylic and hydroxycarboxylic acids
(Wardell and King, 1978; Wennersten, 1983). Re-
active liquid–liquid extraction has the advantage
that lactic acid can be removed easily from the
fermentation broth, preventing the lowering of
pH. Further, the lactic acid can be re-extracted
and the extractant recycled to the fermentation
process.
Organic bases or amine extractants can provide
much higher equilibrium distribution coefficients
(KD) for extraction of carboxylic acids than con-
ventional solvents. Solvent extraction with tertiary
amines has been widely used to recover fraction-
ate metals such as uranium, iron, cobalt, etc. from
aqueous solutions. Most of these extractions are
essentially ion-exchange extractions, because the
amine group is protonated in sufficiently acidic
solutions and forms an ion pair with a metal that
is present in anionic form (Baniel et al., 1981).
Tertiary amine extractants are effective, with KD
strongly dependent upon the nature of the diluent
used and the concentration of amine in that dilu-
ent (Ricker et al., 1979). The active diluents are
usually divided into three classes: active diluents
containing chlorine atoms (methylene chloride,
1-chlorobutane, chlorobenzene, chloroform), car-
bon-bonded oxygen donor active diluents (methyl
isobutyl ketone (MIBK), 1-octanol, 1-decanol)
and phosphorous-bonded oxygen donor active
diluents (tri butyl phosphate) (Han and Hong,
1996).
 K.L. Wasewar et al. / Journal of Biotechnology 97 (2002) 59–68
Tertiary amines are found to be effective in
extracting lactic acid and alcohols are among the
best diluents, with the additional advantage that a
lactic acid ester can be produced after the extrac-
tion process is completed (Ratchford et al., 1951;
King, 1983). Alamine 336 (mixture of C8, C9 and
C10 tertiary amines) yields a good combination of
high KD, low solubility in water and good regen-
erability. The extractant must be diluted with an
organic solvent to provide suitable physical prop-
erties for use in an extraction process. The diluent
also has a strong effect on extraction equilibria
(Wardell and King, 1978). The diluted extractant
gives much higher KD values than the pure
extractant.
The design of an amine extraction process re-
quires (i) equilibrium and (ii) kinetic data for the
acid –amine (solvent) system used. Considerable
information on the equilibrium of several acid–
amine (solvent) systems is available in the litera-
ture. However, no information pertaining to
kinetics is available. In view of this it was thought
desirable to obtain the kinetics of extraction of
lactic acid from aqueous solutions using alamine
336 in MIBK.
This research work reports the liquid– liquid
equilibrium data and kinetics for the extraction of
lactic acid by alamine 336 (a tertiary amine, with
aliphatic chains of 8– 10 carbon groups) dissolved
in MIBK, as diluents.
2. Materials and methods
2.1. Materials
All the chemicals used (lactic acid, MIBK,
sodium hydroxide) were of reagent grade and
were used without pretreatment. All solutions of
lactic acid were prepared by dissolving lactic acid
of analytical purity in distilled water. The initial
concentration of lactic acid was varied from 1.6
kmol m − 3 to 0.088 kmol m − 3. Comparatively
low concentration range was used because in the
practical case of acid recovery from fermentation
broths, the acid concentrations are not expected
to be high.
61
The reactive component was alamine 336
(straight chain tertiary amine containing C8 –C10
alkyl groups (Henkel Corp., USA) with MIBK as
diluent). Alamine was used as supplied.
2.2. Methods
2.2.1. Equilibria
All experiments were carried out at room tem-
perature at 25 °C. Known volumes of aqueous
(different concentrations of lactic acid) and or-
ganic phases (50 ml each) (both pure MIBK and
MIBK containing different concentrations of
alamine 336) of known concentrations were equi-
librated in a temperature-controlled shaker bath
for 24 h. The two phases were allowed to settle
for at least 30 min, which was a sufficient time for
a complete phase separation (San-Martin et al.,
1992). To determine the concentration of lactic
acid, the aqueous phase was titrated with 0.1 N
NaOH and phenolphthalein as an indicator. The
acid concentrations in the organic phase were
calculated by mass balance.
2.2.2. Kinetics
A stirred cell of 0.07 m in diameter and 0.1 m in
height, with a flat bottom was used for the kinetic
studies (Doraiswamy and Sharma, 1984).
Aqueous solution of lactic acid (0.1 m3) of known
concentration was first placed in the vessel. The
position of the four-blade paddle (0.058 m in
diameter and 0.01 mm in width) double stirrer
was adjusted to 1 cm below and above the inter-
face. A fixed volume of the organic extractant
mixture (0.1 m3) was then added, and stirring was
started. Using acid–base titration with 0.1 N
NaOH and phenolphthalein as an indicator, acid
concentration in aqueous phase was determined
periodically. Concentration of lactic acid in the
organic phase was determined by mass balance.
2.3. Theory of extraction accompanied by a
chemical reaction
Doraiswamy and Sharma (1984) have given an
exhaustive discussion on the theory of extraction
accompanied by a chemical reaction (Doraiswamy
and Sharma, 1984). Four regimes of extraction
62 K.L. Wasewar et al. / Journal of Biotechnology 97 (2002) 59–68
accompanied by reaction have been identified de-
pending upon the physico-chemical and hydrody-
namic parameters. When the reaction is reversible
the solute has a finite equilibrium concentration in
the bulk and the driving force needs to be
modified by incorporating the equilibrium con-
centration. The extraction involves the partition-
ing of the solute available in the aqueous phase to
the organic phase.
Aaq “Aorg
The solute A present in the organic phase com-
bines with the organic reactant (amine), B accord-
ing to
A +zBUComplex
Doraiswamy and Sharma (1984) have given the
guidelines for discerning the mechanism in stirred
cell. The hydrodynamic factors (as signified by the
speed of agitation in a stirred cell) are unimpor-
tant in Regimes 1 and 3 whereas the speed of
agitation affects the rate of extraction in Regimes
2 and 4. The expressions for the rate of extraction
for various regimes are given by Doraiswamy and
Sharma (1984). The expression for Regime 3,
extraction accompanied by a fast general order
chemical reaction occurring in the diffusion film is
RA = [A*]
' 2
D k [A*]m − 1[B0]n
m +1 A mn
3. Results and discussion
3.1. Extraction equilibria
Experiments were carried out to describe the
physical and chemical equilibria for lactic acid.
There is only a very slight effect, if any, of
temperature in the range of 20– 90 °C on the
distribution ratio of lactic acid into alcohols, ke-
tones, diethyl carbinol and ethers (Kertes and
King, 1986). The physical equilibrium distribution
isotherm was measured at 25 °C in MIBK. The
results are shown in Fig. 1.
The chemical equilibrium distribution isotherms
, 30% v/v alamine 336 in
were measured at 25 °C for alamine 336 concen-
trations of 20, 30 and 40% v/v in MIBK. The
chemical equilibrium isotherms are shown in Fig.
1. It was observed that extraction efficiency in-
creased with an increase in alamine 336 concen-
tration. San-Martin et al. (1992, 1996) have
reported that the degree of extraction increased
up to a concentration of 40% v/v of the alamine
336 and then remained constant (San-Martin et
al., 1992, 1996).
The reactive liquid–liquid extraction of lactic
acid (HL) with the tertiary amine alamine 336 (B)
gives a reaction complex (BHL) which remains
largely in the organic phase and may be repre-
sented by:
HLw + Bo l BHLo (2)
The distribution coefficient, KD is defined by:
KD = [HL]o/[HL]w (3)
Distribution coefficients obtained by a statisti-
cal analysis of the equilibrium data at low concen-
tration of lactic acid for various alamine
concentrations in MIBK are given in Table 1.
A quantitative interpretation of the equilibrium
for the acid–amine extraction may be defining by
equilibrium complexation constant, KE as:
KE = [BHL]o/[HL]w[B]o (4)
(1)
The concentration of free amine in the organic
phase would be:
Fig. 1. Equilibrium isotherms for reactive extraction of lactic
acid with various concentrations of alamine 336 in MIBK. ,
40% v/v alamine 336 in MIBK.
MIBK. , 20% v/v alamine 336 in MIBK. ", 0% v/v alamine
336 in MIBK.
 K.L. Wasewar et al. / Journal of Biotechnology 97 (2002) 59–68 63

Table 1
Distribution coefficient for the lactic acid extraction with
various concentrations of alamine 336 in MIBK

% Alamine 336 Distribution coefficient (KD)

0 0.31
20 0.72
30 2.68
40 4.24

[B]o = [B]i,o − [BHL]o (5)

If 1:1 lactic acid–alamine 336 complex is Fig. 3. Plot of z/(1− z) vs. [HL]w for the estimation of (1:1)
formed then [HL]o =[BHL]o, lactic acid –alamine 336 equilibrium complexation constant.
K21
log KD =log KE +log[B]o (6)
HLw + BHLo l B(HL)2,o (8)
If the former assumption is valid, a plot of
:
log KD versus log[B]o should yield a straight line
Kn 1
with a slope of unity. As shown in Fig. 2 the HLw + B(HL)n − 1,o l B(HL)n,o (9)
slope is far less than unity (0.2), which implies
that the organic phase extracts more acid than The equilibrium complexation constant for the
would be expected on the basis of 1:1 complex. reaction represented by above equations is:
Hence, the extraction equilibrium of the lactic
[B(HL)n ]o
acid is not adequately represented by Eq. (2). KEn = (10)
Though the exact nature of the chemistry in- [B]o[HL]nw
volved in the uptake of extra acid is known, The extent to which the organic phase
and, in spite of the obvious non-ideality of the (alamine 336+MIBK) can be loaded with lactic
organic phase, distribution data can be inter- acid is expressed as the loading ratio, z;
preted by a set of equilibria involving the for-
mation of complexes with n acid molecules and [HL]o
z= (11)
one amine molecule (Tamada et al., 1990a,b): [B]i,o
K11
HLw +Bo l BHLo (7) The value of z depends on the extractability
of the acid (strength of the acid–base interac-
tion) and its aqueous concentration, and is inde-
pendent of the amine content in an inert diluent
(Kertes and King, 1986; Tamada et al.,
1990a,b).
The stoichiometry of the overall extraction re-
action depends on the loading ratio in the or-
ganic phase, z. If the organic phase is not highly
concentrated, i.e. at very low loading ratios (zB
0.5), the (1:1) complex is formed and a plot of
z/(1− z) versus [HL]w is a straight line whose
slope gives the complexation constant KE in Eq.
(4) and KE1 in Eq. (10).
Fig. 2. Distribution coefficient of lactic acid in alamine dis-
z
solved in MIBK as a function of free amine concentration in =KE1[HL]w (12)
organic phase. 1−z
64 K.L. Wasewar et al. / Journal of Biotechnology 97 (2002) 59–68
A straight line of the plot of Eq. (12) is shown
in Fig. 3 with a slope of 10.15. Hence, the equi-
librium complexation constant for the (1:1) com-
plex at 25 °C for the extraction of lactic acid with
alamine 336 dissolved in MIBK, for low concen-
trations of lactic acid in the organic phase is:
KE1 =10.15 m3 kmol − 1
For higher loading ratios, the (2:1) complex is
formed, and a plot of z/(2 −z) versus [HL]2w
should yield a straight line, whose slope gives the
complexation constant for the (2:1) complex. KE2
is obtained from Eq. (10).
z Figs. 3 and 4 allow the determination of the
= KE2[HL]2w (13)
2− z
A straight line of the plot of Eq. (13) is shown
in Fig. 4 with a slope of 10.13. Hence, the equi-
librium complexation constant for the (2:1) com-
plex at 25 °C for the extraction of lactic acid with
alamine 336 dissolved in MIBK is:
KE2 =10.13 (m3 kmol − 1)2
If the lactic acid concentration is high enough,
the (3:1) complex may be formed and a plot of
z/(3 −z) versus [HL]3w should yield a straight line,
whose slope gives the complexation constant for
the (3:1) complex. KE3 is obtained from Eq. (10).
z 3.2. Kinetics
= KE3[HL]3w (14)
3−z
In this work the complex is not formed because
the concentration of lactic acid in the organic
Fig. 4. Plot of z/(2−z) vs. [HL]2w for the estimation of (2:1)
lactic acid –alamine 336 equilibrium complexation constant.
Table 2
Concentration range of lactic acid in the aqueous phase at
which one of the complexes formed in the organic phase in
equilibrium
Complex Concentration range (kmol m−3)
(1:1) B0.08
(2:1) 0.09–0.9
phase is not high enough and hence the plot based
on Eq. (14) is not considered. This situation is
frequently encountered in fermentation processes
for production of lactic acid.
concentration range of lactic acid in the aqueous
phase at which one of the complexes formed in
the organic phase in equilibrium is present in a
higher proportion. Results are shown in Table 2.
When lactic acid concentration in the aqueous
phase is within the range indicated in Table 2, the
equilibrium concentration in the organic phase is
high enough to form either the (1:1) or the (2:1)
complexes. For the experimental conditions used
in this work, lactic acid concentration is not high
enough to provide the amount of lactic acid
needed in the organic phase so that the (3:1)
complex can be formed.
3.2.1. Physical mass transfer coefficient
The value of physical mass transfer coefficient
kL is required for confirming the regime of extrac-
tion. This was obtained by conducting physical
extraction (diluent only) of lactic acid from water.
For a batch process a differential mass balance
yields the following equation,
dCorg
Vaq = kLAC(C*org − Corg) (15)
dt
Integration of this equation yields,
kL =
Vaq & Corg
dCorg
(16)
ACt 0 (C*org − Corg)
The value of kL evaluated using Eq. (16) for
different speeds of agitation is plotted in Fig. 5.
The regression relation between the mass transfer
 K.L. Wasewar et al. / Journal of Biotechnology 97 (2002) 59–68
coefficient and the speed of agitation obtained by
a statistical analysis data is given below.
kL = 3.5× 10 − 5 N 4.7
The reaction between lactic acid and alamine
336 is reversible, particularly under conditions of
high loading in the organic phase. To avoid prob-
lems due to this reversibility, only initial rates
were considered for evaluation of the kinetics.
3.2.2. Reaction regime
3.2.2.1. Effect of speed of agitation. To find out
the reaction regime, discerning the mechanism
proposed by Doraiswamy and Sharma (1984) was
used. The speed of agitation was varied from 0.65
rev s − 1 to 1.4 rev s − 1. In this range the liquid–
liquid interface was flat and the interfacial area
for extraction was equal to the geometric area.
Fig. 6 indicates that there was no effect of speed
of agitation on the specific rate of extraction, RA
(kmol/m2s). This situation is possible if either
Regime 1 or Regime 3 is valid.
3.2.2.2. Effect of phase 6olume. To differentiate
between Regimes 1 and 3, the effect of organic
phase volume on the specific rate of extraction
was studied. Fig. 7 shows the plot of RA versus
phase volume ratio (volume of organic phase/vol-
ume of aqueous phase) at a constant speed of
agitation. Evidently, there is no effect of phase
volume.
Fig. 5. Effect of speed of agitation on mass transfer coefficient
for the extraction of lactic acid with MIBK.
65
(17)
Fig. 6. Effect of speed of agitation on specific rate of extrac-
tion for the reactive extraction of lactic acid with alamine 336
in MIBK.
From the above experimental results it can be
concluded that the reaction between lactic acid
and alamine 336 in MIBK in a stirred cell falls in
Regime 3, extraction accompanied by a fast chem-
ical reaction occurring in the diffusion film.
3.2.3. Order of reaction
3.2.3.1. Order with respect to lactic acid. The
aqueous phase lactic acid concentration was
varied from 0.1 kmol m − 3 to 0.25 kmol m − 3. Fig.
8 shows the effect of organic phase lactic acid
concentration on specific rate of extraction, RA. A
regression analysis of the data yielded m= 1 (as
per Eq. (1)). Thus, the reaction is first order with
respect to lactic acid.
Fig. 7. Effect of phase ratio on the specific rate of extraction
for the reactive extraction of lactic acid with alamine 336 in
MIBK.
66 K.L. Wasewar et al. / Journal of Biotechnology 97 (2002) 59–68
(DAk1)/kL
Fig. 8. Effect of initial lactic acid concentration on specific rate
(DAk1)/kL $ 8
of extraction for the reactive extraction of lactic acid with
alamine 336 in MIBK.
3.2.4. Order with respect to alamine 336
Fig. 9 shows a plot of the specific rate of
extraction of lactic acid against initial alamine 336
concentration in the organic phase. Evidently
there is no effect of alamine 336 concentration on
the rate of extraction indicating that the reaction
is zero order in alamine 336 (n =0 in Eq. (1)).
3.2.5. Rate constant
For m =1 and n= 0 (Eq. (1)), the rate expres-
sion for the initial part of the extraction is re-
duced to
RA = C*org
DAk1 (18)
Fig. 9. Effect of initial alamine 336 concentration on specific
rate of extraction for the reactive extraction of lactic acid with
alamine 336 in MIBK.
The value of DA was estimated using Wilke–
Chang (1955) equation as 1.16×10 − 9 m2 s − 1.
The data were fitted (Fig. 8) to the above equa-
tion to obtain the value of the first order rate
constant, k1 as 1.38 s − 1.
To confirm that Regime 3 holds the value of
the parameter
was evaluated (Doraiswamy and Sharma, 1984).
It was found that for the range of kL values (Fig.
5)
or greater than 3 which is the condition for the
validity of Regime 3. Thus, the above mentioned
results reflect the true intrinsic kinetics of the
extraction process.
It is generally expected that the reaction be-
tween a carboxylic acid and amine should be
instantaneous, particularly when the reaction
takes place in an aqueous medium where both
species are likely to be in ionic form. However, in
the present case the solubility of lactic acid in the
organic phase is higher than that in water. On the
other hand the organic amine has practically neg-
ligible solubility in the aqueous phase (Ricker et
al., 1980). Thus, there is reason to believe that the
reaction takes place in the organic phase where
ionized species do not exist. This argument fur-
ther supports the finite kinetics observed in the
stirred cell experiments.
4. Conclusion
The extraction of lactic acid from aqueous solu-
tions by alamine 336 dissolved in MIBK was
studied. Physical and chemical equilibria for lactic
acid extraction by alamine 336 in MIBK as a
diluent have been determined. The extent to
which the organic phase (amine+ MIBK) may be
loaded with lactic acid is expressed as a loading
ratio, z= Corg/CB. Calculations based on the stoi-
chiometry of the reactive extraction and the equi-
libria involved indicated that more lactic acid is
transferred to the organic phase than would be
expected from a 1:1 stoichiometry of the reaction.
 K.L. Wasewar et al. / Journal of Biotechnology 97 (2002) 59–68
The extraction equilibrium was interpreted as a
result of consecutive formation of two acid–
amine species with stoichiometries of 1:1 and 2:1.
Equilibrium complexation constants for (1:1) and
(2:1) have been estimated.
In the first study of its kind, the theory of
extraction accompanied by chemical reaction has
been used to obtain kinetics of extraction of lactic
acid by alamine 336 in MIBK. The theory of
extraction accompanied by a chemical reaction
has been used to obtain the intrinsic kinetics of
extraction by alamine 336 in MIBK. The reaction
between lactic acid and alamine 336 in MIBK in a
stirred cell falls in Regime 3, extraction accompa-
nied by a fast chemical reaction occurring in the
diffusion film. The reaction has been found to be
zero order in alamine 336 and first order in lactic
acid with a rate constant of 1.38 s − 1. These data
will be useful in the design of extraction processes.
Appendix A. Nomenclature
[A]* equilibrium concentration in or-
ganic phase (kmol m−3)
AC cross sectional area of stirred cell
(m2)
[B]i,o initial alamine concentration in
the organic phase (kmol m−3)
[B]o alamine concentration remain in
the organic phase (kmol m−3)
[BHL]o (1:1) lactic acid–alamine complex
concentration in organic phase
(kmol m−3)
CA, [LH]w lactic acid concentration in
aqueous phase (kmol m−3)
C *A equilibrium lactic acid concentra-
tion in organic phase (kmol m−3)
Corg lactic acid concentration in or-
ganic phase (kmol m−3)
C *org equilibrium lactic acid concentra-
tion in diluent only (kmol m−3)
DA diffusivity of solute A (lactic
acid) in solvent (MIBK) (m2 s−1)
KE, KE1 (1:1) lactic acid–alamine equi-
librium complexation constant
(m3 kmol−1)
67
KE2 (2:1) lactic acid–alamine equi-
librium complexation constant
(m3 kmol−1)2
KE3 (3:1) lactic acid–alamine equi-
librium complexation constant
(m3 kmol−1)3
[HL]o lactic acid concentration in or-
ganic phase (kmol m−3)
k1 first order rate constant (s−1)
kL overall mass transfer coefficient
(m s−1)
KD distribution coefficient
kmn rate constant for a reaction that
is mth order in species A and nth
order in species B
N speed of agitation (rev s−1)
RA specific rate of extraction of lactic
acid (kmol m−2 s−1)
t time of extraction (s)
Vaq volume of aqueous phase (m3)
z loading ratio (kmol lactic acid
kmol amine−1)
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